Certain phosphorous compounds used as insecticides, miticides and fungicides

ABSTRACT

An insecticidal, miticidal and fungicidal composition comprising as an active ingredient an insecticidally, miticidally and fungicidally effective amount of a compound of the formula: IN WHICH R and R&#39;&#39;&#39;&#39; are lower alkyl, R&#39;&#39;&#39;&#39; is selected from the group consisting of phenyl, lower alkyl-substituted phenyl, chlorine-substituted phenyl and nitro substituted phenyl, and X is selected from the group consisting of oxygen and sulfur, in the presence of an inert diluent.

United States Patent Nishimura et al.

[ 51 Sept. 19,1972

CERTAIN PHOSPHOROUS COMPOUNDS USED AS INSECTICIDES, MITICIDES ANDFUNGICIDES Appl. No.: 866,381

Foreign Application Priority Data Dec. 19,1966 Japan ..4l/82,689 July31, 1967 Japan ..43/48,778

Related 0.8. Application Data Continuation-impart of Ser. No. 680,970,Nov. 6, 1967, abandoned.

US. Cl ..424/212, 260/941 Int. Cl. ..A0ln 9/36 Field of Search..424/212; 260/941 References Cited .UNlTED STATES PATENTS 12/1957Schuler ..424/212 3,228,999 1/ 1966 Schicke ..260/940 PrimaryExaminer-Albert T. Meyers Assistant Examiner-Leonard SchenkmanAttorney-Stevens, Davis, Miller & Mosher 5 7] ABSTRACT An insecticidal,miticidal and fungicidal composition comprising as an active ingredientan insecticidally, miticidally and fungicidally effective amount of acompound of the formula:

in which R and R" are lower alkyl, R" is selected from the groupconsisting of phenyl, lower alkyl-substituted phenyl,chlorine-substituted phenyl and nitro substituted phenyl, and X isselected from the group consisting of oxygen and sulfur, in the presenceof an inert diluent.

12 Claims, No Drawings CERTAIN PHOSPHOROUS COMPOUNDS USED ASINSECTICIDES, MITICIDES AND FUNGICIDES This application is acontinuation-in-part of our copending application, Ser. No. 680,970filed Nov. 6,

1967 now abandoned.

The present invention relates to compositions for preventing harmfulorganisms of fungi, mites and insects comprising as active ingredientnovel organic phosphates having the general formula R coon" wherein Rand R" represent lower alkyl groups, R represents a group selected fromthe class consisting of phenyl, lower alkyl-substituted phenyl,chlorine-substituted phenyl, nitro substituted phenyl and X representsan atom selected from the group consisting of oxygen and sulfur, and amethod of using these compositions.

It is known that alkyl-dialkoxyphosphinylthio-alkylthioacetates are usedas compositions for combating insect pests and their manufacture isdisclosed in US. Pat. No. 2,815,312. It has now been found that thephosphorus compounds according to the present invention show improvedinsecticidal properties. They distinguish themselves further by a verygood acaricidal action in residual effectiveness and a very goodfungicidal action at minimum rates of application.

The active ingredients according to the present invention are novelorganophosphorus compounds having a low toxicity against warm bloodedanimals and show an excellent insecticidal activity against harmfulinsects for agricultural products.

Moreover, the phosphorus compounds according to the present inventioncan be used as a fungicide, particularly, a composition for preventingrice blast (Piricularia Oryzae) instead of organomercurous com poundspreviously used.

ROX

COOR

R0 R0 000R" wherein R, R, R" and X have the same meanings as describedabove and M represents a material selected from the group consisting ofalkali metals and ammoni- The active ingredients produced by the abovedescribed reaction formula are listed as follows:

'1. ethyl-a-(diethoxyphosphinylthio)-a-(phenylthio) acetate 2.ethyl-a-(diethoxyphosphinylthio )-a-(4- chlorophenylthio) acetate 3.ethyl-a-(dimethoxyphosphinylthio )-a-( 4- chlorophenylthio) acetateethyl-a-(diethoxyphosphinylthio)-a-(4- methylphenylthio) acetate 5.ethyl-a-(dimethoxyphosphinylthio)-a-(4- methylphenylthio) acetate 6.n-propyl-a-(dimethoxyphosphinylthio)-a-(phenylthio) acetateethyl-a-(dimethoxyphosphinothioylthio)-a-(4- chlorophenylthio) acetate8. ethyl-a-( diethoxyphosphinothioylthio )-a-(4- methylphenylthio)acetate ethyl-a-(diisopropoxyphosphinylthio )-a-( 4- chlorophenylthio)acetate 10. ethyl-a-(diisopropoxyphosphinothioylthio)-a-(4-chlorophenylthio) acetate Compounds 1, 2 described hereinafter mean thecompounds 1, 2 disclosed in the above list. Then, the present inventionwill be explained with respect to examples for synthesizing thecompounds according to the present invention.

EXAMPLE 1 Ethyl-a-( diethoxyphosphinylthio)-a- (Phenythio) Acetate Asolution of 20.8 g (0.1 mole) of potassium 0.0- diethylthiolophosphatein 200 ml of acetone was ,introduced into 300 ml of three-necked flaskand added gradually with 23.1 g (0.1 mole) of ethyl-achloro-a-(phenylthio) acetate (boiling point of CJmm Hg) dropwise, while stirringthoroughly. After completed the addition, the resulting mixture washeated and circulated for 3 hours.

After the reaction was completed, the precipitated potassium chloridewas filtered off and the filtrate was distilled to remove acetone andthe residual oil layer was extracted with benzene, and then the extractwas washed with water and dried with anhydrous Glaubers salt. Benzenewas distilled off and the residue was subjected to a high vacuumdistillation to obtain 27.5 g of a fraction having a boiling point of toC./0.01

to 0.02 mm Hg, which was yellow clear liquid. Yield 75.6 percent.Refractive index N 1.5330.

Elementary analysis Found, P 8.38%, Calculated, P 8.48%.

LR. Absorption band shows phenyl 3,060 cm (W), 1,580 cm, 1,475 cm (M), CH 2,9802,985 cm, 1,440 cm, C0 1,745 cm, PO 1,255 cmi, (C H O)2P 1,015970 cm.

Compound Nos. 2 to 49.were produced in the same manner as describedabove.

Furthermore, the compounds having the general formula, which are thestarting material for the above synthesis, can be produced by thefollowing reaction formula:

RSCl N=NCHCOOR" Cl-CH --SR' N2 COOR" The phosphoric acid estersaccording to the present invention are mixed with a diluent involvingcarriers and surfactants to prepare dusts, emulsifiable concentrates,wettable powders, which can be used directly or after diluted withwater.

The term carrier used herein means vehicles to be used for carrying theactive component to a desired area, which may be both solid and liquid.

For example, as solid carriers use may be made of various clays, talc,kaolin, diatomaceous earth, calcium carbonate, white carbon and sawdust. As liquid carriers, use may be made of solvents for the activecomponents and non-solvents which can disperse or dis solve the activecomponent by means of an auxiliary agent, for example, water, benzene,kerosine, alcohols, acetones, methylnaphthalene, xylene.

The term surfactant" used herein involves no'nionic sufactants, such aspolyoxyethylenesorbitan monolaurate, etc., cationic surfactants, such asalkyldimethylbenzylammonium chloride, alkylpyridinium halide, etc.,anionic surfactants, such as alkylbenzenesulfonate, higher fatty alcoholsulfate, etc., amphoteric surfactants, such as lauryl amine derivatives,betaine derivatives, dodecyldiaminoethyl glycine, etc.

The invention will be explained further with respect to some preparationexamples, but the diluents, the mixture ratios and the active componentscan be varied in a wide range. The percent means by weight.

EXAMPLE 2 Dust Two of ethyla-(dimethoxyphosphinylthio)-a-(4-chlorophenylthio) acetate, percent of diatomaceous earth, 50 percent ofkaolin and 43 percent of talc were mixed and pulverized, and theresulting powder was dusted.

EXAMPLE 3 Wettable Powder Twenty percent ofethyl-a-(dimethoxyphosphinothioylthio)-a-(4-chlorophenylthio) acetate,percent of diatomaceous earth, 55 percent of kaolin and 5 percent of amixture of polyoxyethylene alkylphenyl ether, polyoxyethylenephenylphenol ether and polyoxyethylene carboxylate, which is a spreadingagent, were mixed and pulverized to form a wettable powder, which wasused as an emulsion in water.

EXAMPLE 4 Emulsifiable Concentrate Twenty percent ofethyl-a-(diethoxyphosphinylthio)-a-(phenylthio) acetate, 60 percent ofxylene,

20 percent of a mixture of polyoxyethylene alkylphenyl ether,polyoxyethylene phenylphenol ether and polyoxyethylene carboxylate,which is an emulsifier, were mixed and dissolved to obtain anemulsifiable concentrate, which was used after diluted with water.

EXAMPLE 5 Dust Two'percent of ethyl-a-(diethoxyphosphinylthio)-a-(phenylthio) acetate,'5 percent of diatomaceous earth, 50 percent ofkaolin and 43 percent of talc were mixed and pulverized to form a dust,which was dusted.

EXAMPLE 6 Wettable Powder Twenty percent ofethyl-a-(diethoxyphosphinylthio)-a-(4-chlorophenylthio) acetate, 20percent of diatomaceous earth, 55 percent of kaolin and 5 percent of amixture of polyoxyethylene alkylphenyl ether, polyoxyethylenephenylphenol ether and polyoxyethylene carboxylate, which is a spreadingagent, were mixed and pulverized to form a wettable powder, which wasused as a suspension in water.

EXAMPLE 7 Emulsifiable Concentrate Twenty percent ofethyl-a-(dimethoxyphosphinothioylthio)-a-(4-chlorophenylthio) acetate,60 percent of xylene and 20 percent of a mixture of polyoxyethylenealkylphenyl ether, polyoxyethylene phenylphenol ether andpolyoxyethylene carboxylate, which is an emulsifier, were mixed anddissolved to form an emulsifiable concentrate, which was used afterdiluted with water.

Then Experimental Examples for preventing disease and insect pests bymeans of the active compounds according to the present invention will beexplained.

Experimental Example 1 Test for controlling Panonychus ulmi Koch ActiveingredientzCompounds are shown in the following Table 1.

Concentration: l ,000 ppm in phosphorus series compounds; l ppm in thecomparative compound made by Nippon Soda Kabushiki Kaisha under thetrademark Nisol, which was prepared by diluting 35 percent of wettablepowder of this compound to 2,000 times.

Test method:A branch of an apple tree (length 25 cm, number of leaves;5-6) infested with the adults of Panonychus ulmi Koch was cut and putinto a glass bottle. Each 20 cc of an aqueous dispersion of the compoundto be tested, which was adjusted to the predetermined concentration, wasspread on the branch by means of a glass nozzle. Two days after spread,the mortality was determined to obtain the results as shown in thefollowing Table l.

TABLE 1 Insecticidal uctlvlty Number of adults to be tested Number ofliving Active ingredient adults Mortality Compounds in the invention:

Comparative compounds:

CH O

OOCzHs CHaO S \H /P-SCH-SCH H9 98 19.3 CHgO (L OOCzHs CHaO\fiPSCHS-CHz-Cl 01 to 83.6 CH/ OOC H (H) /CH: FCH CN\ I (Nisol) Non-treated42 39 7. 2

Test method:A branch of an apple tree (length 20 cm, number of leaves;4-5) infested with the adults of Panonychus ulmi Koch was cut and putinto a glass bottle. Each 15 cc of an aqueous dispersion of the compoundto be tested which was adjusted to the predetermined concentration,was'spread Experimental Example 2 Test for controlling Panonychus' ulmiKoch Active ingredientzCompounds are shown in the following Table 2.Concentration: l ,000 ppm in phosphorus series compounds; l75 ppm in thecomparative compound made by Nippon Soda Kabushiki Kaisha under thetrademark Nisol, which was prepared by diluting 35 percent of wettablepowder of this compound to 2,000 times.

on the branch by means of a glass nozzle. Three days after spread, themortality was determined to obtain the results as shown in the followingTable 2.

TABLE 2 Inseetlcldal activity Number of Number adults of to be livingMortal- Actlve ingredient tested adults it? Compounds in the invention:

1' .1' ;Il s I Tte/ J i U:

Uh U '25 0 100.0

Q CHsO (L 0 0 CzH5 CQHLO O 51 0 100. 0

ll '/P--SCHS-- Cl (311-150 1/ ll /PSCHS Cl OH O O O CZHs CHSO 0 63 0100. 0

P-SCH- S Comparative compounds:

c,H,,0\ls| 40 16 56. 7

/P-S-CH-S-OH CzH50 O 0 C3115 Nisol 34 o 100. o Non-treated 56 54 3.

Experimental Example 3 Test for controlling Panonychus ulmi Koch Activeingredient and concentration:

For each of phosphorus series compounds, 10 percent wettable powder wasused and diluted with water into each concentration of 500 ppm. ForNisol, 25 percent wettable powder was used and diluted with water to1,500 times. Test method:

TABLE 3 Number of insects Number after spreading of insects Concenbefore1 6 9 Active ingredient tratlon spreading day days days Compound in theinvention:

(3,1[ 0 O 500p.p.in 34 l l 0 mum Fungicidal activity against rice blastFor rice plants of Aichiasahi variety were grown in each pot having adiameter of IS cm and the plants 55 were sprayed with each aqueousdispersion prepared by diluting the wettable powder of the compoundsshown in the following Table 4 to the concentration as described inTable 4 at the young ears formation period. The pots on a turntableTABLE 3 Number 01 lnsocls N umber nltor sprundlng ol insects(foncunbulom l (l 9 Active ingredient tratlon sprundlng dny days daysC1H5O\fi 500 p.p.m. 39 0 0 PSCHSC m CzHgO l CH30\|0| B00 p.plm 39 0 0 0IS--C HSC H: C H3O I CH3O\?I) 500 p.p.m... 30 11 0 1 C H30 I C O0-C1H4CH3 CzH50\fi 500 ptp.1'n 35 16 0 0 /PSCH-S-Cl 02 50 I C 0 OCgH4-CH3 C H;0\(") I 500 p.p.m. 31 0 0 P--S-CH-SCl I C H3O C O OCzHr-CH:

Comparative compounds:

C2Hs0\fi 600 p.p.m.. 21 16 5 5 P-S-C HSC1Ha 0,11 0 0 O 0 CzHs CHaO (If500p.p.m 21 14 8 8 PS(]JH-SC:Hs CHaO COOCzHs 4 p MM" v M A 0,H,0 soop.p.m... is 14 7 7 P-s-pH-s-cH,-ci 0,1150 000mm C:Hs0\fi 500 p.p.m 30 2322 18 l=-spn-scmci CgHsO C 0 0 05H;

CHa0\(]? 500 p.p.m. 37 21 19 /P s -pH- s -omci 0 H 0 0 0 0 CzHs CHa0\(")500 p.p.m... 31 25 15 15 PSCHS-CHs CH CO0C H CH:

CgH\i 600 p.p.m.. 33 18 12 7 P-S-CH-S-CHs CzHsO C O O CgHs CHsO S 500p.p.m. 37 11 3 3 S -(|JHS -CHa CH O C 0 O CaHs Nlsol l, 500 times. 30 00 0 Nisol ..d0 32 0 0 0 EXPERIMENTAL EXAMPLE 4 M were sprayed by meansof pressure sprayer from the side, until the leaves were wettedthoroughly. On the next day, the rice plants were inoculated by means ofspraying a spore suspension of Pyricu- Iaria Oryzae collected from thedisease leaves. Treated pots were kept in the moisture chamber ofgreenhouse. One week after the inoculation, the number of the diseasedspots in the upper leaves EXPERIMENTAL EXAMPLE 5 compound as shown inthe following Table 5 was diluted with water into the concentrationsasshown, in

Residual effectiveness against citrus red mite the following Table 5 andthen spread on summer orange seedlings infested with citrus red mite.After 5 spread, thenumber of living mites was measured and the resultsare shown in the following Table 5.

TABLE 6 Number oi living mites Concen- Before 2 days 6 days 7 days 10days 14 days 19 days tration spreading aiter aiter aiter after aiteralter Active ingredient (percent) spreading spreading spreadingspreading spreading spreading Compound in the invention:

C H O\(") 0. 05 38 i 0 1 5 37 s 8 C H 0 CzHuO 0 0. 06 68 0 0 0 0 l7 8 i-s -CH-S-C1 l CaHs l C O 0 cgHi 011,0 0 0. 05 a4 0 1 1 a a a2 i S-CHS'ClCH 0 i Cl 0. 06 42 0 0 1 8 10 47 CaHsO O PS CH- 8- CzHsO C O 0 Cal-Is01110 s 0. 05 e1 1 1 0 s 14 a2 i SCHS c1 CH 0 i isoC1H10 O 0. 06 34 1 10 1 a 48 i s-cn-s-Q-ci 1500 H 0 i r coociHi a Comparative compounds:

CHs0\(l? 0. 06 86 43 32 18 37 68 /-P-S-CH-SCH: CHaO 0 O 02H.

CHgO O CH: 0. 05 72 11 10 24 28 42 51 /PS--(I3HSCH CH;O COOCaHs CH:

CgHso 8 CH; 0. 05 31 7 18 14 19 24 47 P- S-CH-S-C CzHsO COQCpHu CH8 OHO\fi 0. 06 29 27 29 18 15 26 80 /PSCHS-C|Hs 0 H30 0 0 C235 OHaO\(") 0.05 108 62 62 88 19 56 C H1O C .0 Q 02H:

Kelthane 0.02 86 0 0 0 2 0 2 Non-treated 33 64 61 107 47 32 f 1, 1-lais(p-chlorophanyl)-2, 2, 2-trichioroeti1ano1 made by ltoiun and Haas00. under the trademark Kelthane."

EXPERIMENTAL EXAMPLE 6 Effectiveness against the larvae of rice stemborer, Chilo suppressalis Walker.

Each liquid having the concentration of the compounds as shown in thefollowing Table 6 was spread on rice plant, the stem of which had beenencroached by stem borer 7 days ago, and the mortality was determined toobtain the result as shown in Table TABLE 7 Active ingredient Altersprayed 1 day '2 days 3 days Numberof Mortality Number of MortalityNumbero! Mortality insects (percent) insects (percent) insects (percent)Conkpound in the invention:

A: ethyl-a-(diethoxyphosphinylthio)-a-(phenylthio)acetate.

B: ethyl-a-(dimethoxyphosphinylthio)-a-(phenylthio)acetete.

C: ethyl-w(dimethoxyphosphinylthio)-a-(2,o-dichloro heny1thio)acetate.11g: ethyl-a-(dimethoxyphospbinylthio)-a-(methylthio acetate.

: ethyl-a-(dimethoxyphosphino h hinylthio)-a-(ethyithio)aoetate. ospinylthio)-a-(ethylthio)acetate.

: ethyi-a-(dimethoxy ethyl-a-(diethoxypl:

TABLE 6 Concentration Mortality Active ingredient (p.p.rn.) (percent)Compound in the invention:

P- S C H- S do our.

C=HO\I) 500 93.8

CsHsO C 0 0 CzHqCHQ (2.11.0 s s00 90. a

I P- s -cH-s- CgHsO ,COOCzIhCH; Comparative compounds:

cmo o s00 00. s

P-s-cll-s-0 rn- (30001115 mun 0 500 01.0

| -s-cil-;-s--0u,

()H O O 0 O CsHrO ll:

OHIO O 600 l2. l5

P-S-CI IS-CsI-Is 0 H30 0 '0 O CQH} EXPERIMENTAL EXAMPLE 7 centrate,which was diluted with water to form a solu- 65 tion having aconcentration of active ingredient of 0.02 percent. ml of the dilutedsolution was sprayed on thioylthio)-a-(isopropylthio)acetate.

What is claimed is: I. An insecticidal, miticidal and fungicidalcomposi- 30 tion comprising as the active ingredient an insecticidally,miticidally and fungicidally effective amount of a compound of theformula:

in which R is selected frdrii group consisting of methyl, ethyl andisopropyl, R' is selected from the group consisting of phenyl,4-methylphenyl, 4-

40 chlorophenyl, 2,5-dichlorophenyl, Z-nitrophenyland 3- nitrophen l R"is an alky l havii g two to three carbo atoms an X is selected rom egroup consisting 0 oxygen and sulfur, and an inert carrier.

2. The composition of claim 1, wherein the com- 5 pound isethyl-a-(diethoxyphosphinylthio)-a-(phenylthio)acetate.

3. The composition of claim 1, wherein the compound isethyl-a-(diethoxyphosphinylthio)-a-(4- chlorophenylthio)acetate.

so 4. The composition of claim 1, wherein thecommethyiphenylthio)acetate.

6. The composition of claim 1, wherein the compound isethyl-a-(dimethoxyphosphinylthio)-a-(4- methylphenylthio)acetate.

7. The composition of claim 1, wherein the compound isn-propyl-a-(dimethoxyphosphinylthio)-a- (phenylthio)acetate.

8. The composition of claim 1, wherein the com pound isethyl-a-(dimethoxyphosphinothioylthio)-a-(4 -CHLOROPHENYLTl-ll0)acetate.

9. The composition of claim I, wherein the com pound isethyl-a-(diethoxyphosphinothioylthio)-a-(4- methylphenylthio )acetate.

it %i121.

in which R is selected from the group consisting of methyl, ethyl andisopropyl, R is selected from the group consisting of phenyl,4-methylphenyl, 4- chlorophenyl, 2,5-dichlorophenyl, 2-nitrophenyl and3- nitrophenyl, R" is an alkyl having two to three carbon atoms and X isselected from the group consisting of oxygen and sulfur; in combinationwith an inert carrier.

2. The composition of claim 1, wherein the compound is ethyl-Alpha-(diethoxyphosphinylthio)- Alpha -(phenylthio)acetate.
 3. Thecomposition of claim 1, wherein the compound is ethyl-Alpha-(diethoxyphosphinylthio)- Alpha -(4-chlorophenylthio)acetate.
 4. Thecomposition of claim 1, wherein the compound is ethyl-Alpha-(dimethoxyphosphinylthio)- Alpha -(4-chlorophenylthio)acetate.
 5. Thecomposition of claim 1, wherein the compound is ethyl-Alpha-(diethoxyphosphinylthio)- Alpha -(4-methylphenylthio)acetate.
 6. Thecomposition of claim 1, wherein the compound is ethyl-Alpha-(dimethoxyphosphinylthio)- Alpha -(4-methylphenylthio)acetate.
 7. Thecomposition of claim 1, wherein the compound is n-propyl-Alpha-(dimethoxyphosphinylthio)- Alpha -(phenylthio)acetate.
 8. Thecomposition of claim 1, wherein the compound is ethyl-Alpha-(dimethoxyphosphinothioylthio)- Alpha -(4-chlorophenylthio)acetate. 9.The composition of claim 1, wherein the compound is ethyl-Alpha-(diethoxyphosphinothioylthio)- Alpha -(4-methylphenylthio)acetate. 10.The composition of claim 1, wherein the compound is ethyl-Alpha-(di-isopropoxyphosphinylthio)- Alpha -(4-chlorophenylthio)acetate 11.The composition of claim 1, wherein the compound is ethyl-Alpha-(di-isopropoxyphosphinothioylthio)- Alpha -(4-chlorophenylthio)acetate.12. A method of controlling and killing insects, mites and fungi whichcomprises applying thereto a pesticidally effective amount of a compoundof the formula: in which R is selected from the group consisting ofmethyl, ethyl and isopropyl, R'' is selected from the group consistingof phenyl, 4-methylphenyl, 4-chlorophenyl, 2,5-dichlorophenyl,2-nitrophenyl and 3-nitrophenyl, R'''' is an alkyl having two to threecarbon atoms and X is selected from the group consisting of oxygen andsulfur, in combination with an inert carrier.